Process for treatment of water and of surfaces in contact with the said water in order to prevent the attachment of and/or to remove and/or to control macroorganisms, composition and paint for the said treatment

ABSTRACT

The invention relates to a process for the treatment of water and of surfaces in contact with the said water in order to prevent the attachment and/or to remove and/or to control macroorganisms, in particular molluscs, on the said surfaces in contact with the water, in which process at least one biocidal and/or biostatic active product is employed which is injected into the water and/or applied to the said surfaces, according to which process the active product(s) used comprise(s) at least one polyamine of formula I: 
     
         R.sub.1 -NH[(CH.sub.2).sub.3 -NH].sub.n -(CH.sub.2).sub.3 NH.sub.2(I) 
    
     in which formula R 1  is a C 8  -C 22  alkyl or alkenyl radical and at least one monoamine of formula II: 
     
         R.sub.2 NH.sub.2                                           (II) 
    
     in which formula R 2  is a C 8-C   22  alkyl or alkenyl radical, and n is an integer between 0 and 3 (inclusive). 
     The invention also relates to a composition to be injected into the water and to a paint for covering the surfaces in contact with the water.

The present invention relates to a process for the treatment of water and of surfaces in contact with the latter in order to prevent the attachment of and/or to remove and/or to control macroorganisms, in particular-molluscs, on the surfaces in contact with water, to a composition to be injected into the water and to a paint to be applied to the surfaces in contact with the water, for the said treatment.

A considerable number of industries make use either of fresh water, such as water from streams, rivers, lakes, natural or artificial reservoirs, wells used in the ground or of other drawn water, or of salt water, such as sea-water. This water is, for example, used in boiler circuits or in cooling-water circuits. The water circulates in the industrial installations in an open circuit, the water being drawn, for example, from a river and subsequently discharged downstream, or in a closed or semi-closed circuit, the water being reused a number of times.

It is known that, on the surfaces of the installations in which the water circulates or is stored, micro-organisms first of all develop, which form on the said surfaces a biological or bacterial film consisting of organic materials, bacteria, algae, protozoa or other microorganisms. This biological film may lead to considerable losses in output, in heat exchangers for example. Moreover, the presence of this biological film may give rise to localized instances of corrosion, which are linked to the physical presence and to the metabolism of the microorganisms making up the said film. Subsequently, macroorganisms also develop on the surfaces in contact with water, which macroorganisms may be algae, molluscs such as mussels, clams and barnacles, serpulae, crustaceans, hydroids, bryozoa and hydrozoa. These macroorganisms form encrustments on the surfaces of the installations which are in contact with water. These encrustments are difficult to remove, and it is often necessary to shut down the installation and to empty it of water before mechanically or manually removing the said encrustments. Attempts have thus been made to introduce into the water, as active products, compounds having a biocidal and/or biostatic action which is capable of preventing the growth of the microorganisms and macroorganisms and their attachment to the surfaces in contact with water.

Numerous compounds termed biocides have been proposed and used for the treatment of water. Those most commonly employed in practice are halogens or halogenated inorganic or organic derivatives, such as chlorine, bromine, iodine, potassium chloride, hypochlorous acid and its sodium or calcium salts, hypobromous acid, the salts of dichloro- and trichloroisocyanuric acids, or halogenated hydantoins however, these compounds have the disadvantage of being corrosive and of forming, with the organic materials present in the water, chlorinated compounds which are highly toxic. It has also been proposed to use peroxygenated derivatives, phenols and phenol derivatives, heavy metals or organic derivatives thereof, formaldehyde, benzoic acid and benzoates for treatments by injection or by contact with a coating. However, the majority of these compounds are expensive, and their use in industrial installations which utilize large quantities of water is inconceivable. Moreover, many of them leave toxic or corrosive residues in the treated water.

The biocidal compounds are generally used in the form of a solution or dispersion in an aqueous phase which may contain organic solvents. In this case they are usually injected into the water to be treated. However, in certain cases, especially when these biocidal compounds are of low solubility in water, they are incorporated in a material, for example a paint, and the material containing the biocidal compound is applied to the surface to be protected, for example the hull of a ship, so as to treat the water in contact with the surface to be protected.

Generally, in order to be suitable for use in an appropriate fashion in a process for the treatment of industrial water, in particular in an open-circuit installation, a biocidal compound must have the properties of:

preventing the corrosion of surfaces in contact with the water, whether this corrosion derives from chemical products present in the water, such as CO₂, or from the biological film,

preventing the formation of the biological film,

eliminating or preventing the attachment of the macroorganisms, and

leaving no toxic or corrosive residue in the water after use, so as to conserve the flora and fauna downstream of the industrial installation.

According to the present invention it has been found that amines, more specifically a particular mixture of polyamines, have all of the above properties, and that they make it possible advantageously to remove macroorganisms, more particularly molluscs, from surfaces in contact with water. More specifically they make it possible to eliminate the problem posed by zebra mussels or Dreissena in industrial installations in which water circulates in an open circuit, such as the cooling installations in thermal or nuclear power stations.

The subject of the present invention is therefore a process for the treatment of water and of surfaces in contact with the latter in order to prevent the attachment of and/or to destroy macroorganisms, in particular molluscs, on the surfaces in contact with the water, in which process at least one active biocidal and/or biostatic product is employed which is injected into the water and/or applied to the said surfaces, characterized in that the active product(s) used comprise(s) at least one polyamine of formula I:

    R.sub.1 -NH[(CH.sub.2).sub.3 -NH].sub.n -(CH.sub.2).sub.3 NH.sub.2(I)

in which formula R₁ is a C₈ -C₂₂ alkyl or alkenyl radical and n is an integer between 0 and 3 (inclusive), and/or at least one monoamine of formula II:

    R.sub.2 NH.sub.2                                           (II)

in which formula R₂ is a C₈ -C₂₂ alkyl or alkenyl radical.

According to the invention, the active product of formula I used is more particularly a mixture containing firstly at least one polyamine of formula I in which R₁ is a dodecyl radical, and/or at least one polyamine of formula I in which R₁ is a tetradecyl radical, and secondly at least one polyamine of formula I in which R₁ is an octadecenyl radical. This mixture may also contain other monoamines and/or polyamines.

According to the present invention, the amines and polyamines are used as such and not in the form of salts.

According to the present invention, the active product (s) may advantageously be injected into the water. According to the invention, the injection into the water of the active product(s) can be made, into the water to be treated, continuously or intermittently. In the first case, an amount required in order to obtain a concentration of between 0.01 and 1.5 ppm of product(s) of formula(e) I and/or II per liter of water may be suitable with regard to the treated surfaces. In the second case, daily injections of product(s) of formula(e) I and/or II such as to obtain a concentration of the order of 6 mg/l for 1.5 hours may bring about the eradication of a population of Dreissena in one month. The required concentrations of active product (s) of formula (e) I and/or II depend on the macroorganisms to be removed, on the size and nature of the surfaces in contact with the water, and on the flow of water, and may readily be determined by a person skilled in the art.

The treatment of the water by the active product(s) is advantageously carried out by injection into the water of a biocidal composition containing all of the active products of formula(e) I and/or II to be employed for the treatment. However, it is possible to envisage separate injections of the different active products to be employed, each injection being carried out with a partial biocidal composition. Further subjects of the invention are the total or partial biocidal compositions employed for the treatment process defined above.

These compositions are in practice preferably obtained by mixing polyamines derived from tallow and/or polyamines derived from a vegetable or animal oil containing olein with polyamines derived from coconut.

For injection into the water the compositions are preferably formulated as an emulsion, or better still a microemulsion, in an aqueous phase, since the amines of formula(e) I and/or II as such are not soluble in water. An emulsifying surfactant is advantageously used in order to emulsify the active product(s). This emulsifier advantageously comprises at least one polyoxyethylenated tertiary amine of formula III: ##STR1## in which formula R₃ is a C₈ -C₂₂ alkyl or alkenyl radical, preferably a hexadecyl, stearyl or oleyl radical, and x and y are integers such that x+y is between 5 and 50, preferably between 10 and 20. The emulsifier may make up from 5 to 45% by weight, preferably from 15 to 35% by weight, relative to the weight of the combination formed by the active product(s) of formula(e) I and/or II.

The aqueous phase may contain at least one organic solvent in addition to the water. This organic solvent is appropriately chosen from the group consisting of diethylene glycol, hexylene glycol, monopropylene glycol and an amino alcohol of formula IV:

    HO-A-NR.sub.4 R.sub.5                                      (IV)

in which formula A is a C₂ -C₄ linear or branched alkenyl radical and R₄ and R₅, which are identical or different, are H or a C₁ -C₃ alkyl radical.

The aqueous phase of the emulsion, including the solvent if appropriate, may make up to 90% by weight of the said emulsion.

According to the present invention, it is also possible to treat the water by applying, to the surfaces in contact with the water, a coating containing at least one active product of formula(e) I and/or II, in particular a paint. According to a particular embodiment of such a paint, at least one active product of formula(e) I and/or II is mixed with a pulverulent filler, for example micronized silica, so as to obtain a pulverulent product which is subsequently introduced into a paint in the same way as a pigment. Another subject of the invention is the paint used for the implementation of this variant of the process.

According to the present invention, it has been found that the polyamines of formula I and the amines of formula II have an activity on the macroorganisms which attach themselves to the surfaces in contact with the water; these macroorganisms may be algae, serpulae, crustaceans, hydroids, bryozoa and hydrozoa, and more specifically molluscs, for example mussels, barnacles and clams. For simplification, this activity against macroorganisms will be denoted, in the remainder of the application, by the term "molluscicidal activity". It has also been found, according to the present invention, that this molluscicidal activity is particularly high when polyamines comprising a fatty chain R₁ which is a dodecyl (or lauryl) chain and/or a tetradecyl (or myristyl) chain are mixed with polyamines comprising an octadecenyl (or oleyl) fatty chain R₁. In effect, there is a synergetic reaction between these two types of polyamines, as shown by the examples given below. This preferred mixture of polyamines may additionally contain other polyamines, without the synergy being altered. This is the case in particular when use is made

either of commercial polyamines of formula I in which the fatty chain is derived from coconut and contains, in addition to the polyamines of formula I having a C₁₂ and C₁₄ fatty chain, polyamines having a C₈, C₁₀, C₁₆, C₁₈, and monounsaturated C₁₈ radical R₁,

or of commercial polyamines of formula I in which the fatty chain is derived from tallow and contains, in addition to the monounsaturated C₁₈ radical R₁, C₁₄, C₁₆ and C₁₈ radicals R₁,

or of commercial polyamines of formula I derived from vegetable or animal oil containing olein, in which the fatty chain comprises, in addition to mono-unsaturated C₁₈ radicals R₁, C₁₄, C₁₆, mono-unsaturated C₁₆ and saturated C₁₈ radicals R₁, and in some cases dienic C₁₈ radicals R₁.

This mixture may also contain amines R₂ NH₂, which are combined with the polyamines of formula I in the commercial products and whose radicals R₂ are generally the same as the radicals R₁ of the polyamines of formula I; in this case, the content of monoamines does not exceed 15% by weight.

Tests have shown that the biocidal composition according to the present invention makes it possible to remove striped mussels (Dreissena polymorpha) in a cooling installation of a thermal or nuclear power station, in which the water circulates in an open circuit, by injecting the composition into the water in the form of a microemulsion. Moreover, it has been found that the composition used in accordance with the invention makes it possible to prevent the attachment of molluscs to the surfaces in contact with the water. In effect, it has been observed in laboratory experiments that the composition used in accordance with the invention brings about an inhibition of the growth of the byssal filaments of striped mussels. A further observation has been the low adherence of barnacles and acorn-shells to the surfaces in contact with the water in the presence of the said biocidal composition.

It is known, furthermore, that the fatty-chain amines used have a stable film-forming effect and that, when injected into the water, they become attached in the form of a film to the surfaces in contact with the water. Consequently the necessary quantities of biocidal composition, when treatment is effected by injection, are low, because the film attached to the surfaces has a long-term action on the micro- and macroorganisms. This is not the case with chlorine and its derivatives (chlorine dioxide and organic chlorine compounds), the compounds which are most generally employed in the prior art, which do not become attached to the surfaces and which spread throughout the body of water. Consequently, according to the treatment process of the invention, the quantity of biocidal composition to be injected into the water depends more on the surfaces in contact with the water than on the flow of water in the installation. In particular, to treat a predetermined surface, it is possible first of all to introduce a relatively high concentration of biocidal composition according to the invention, so as to form the film on the surface, and subsequently to maintain a lower concentration of biocidal composition at the surface to be protected, in order to replenish the film and to act on the macroorganisms.

The biocidal composition used in accordance with the invention also makes it possible to prevent the formation of the biological film or to destroy it when it is formed and to prevent the corrosion caused by this biological film. It also has the anticorrosion action and antiscale action for which amines are known.

The biocidal and anticorrosion action of the biocidal composition used in accordance with the invention has been verified for numerous surfaces of steel, copper, ceramic, glass and plastics, for example.

Moreover, the biocidal composition used is not toxic. In fact, the life of the amines and polyamines in the medium treated is relatively short, and no toxic secondary products are formed. It has been found that the residual water leaving a cooling installation of a power station, the water of which is treated by the process according to the invention, has no toxic action on fish, in particular of young perch and bream.

The compositions used in accordance with the invention are prepared by mixing the constituents. In practice, a particularly appropriate composition is obtained by mixing at least one polyamine derived from coconut with at least one polyamine derived from tallow and/or at least one polyamine derived from a vegetable or animal oil containing olein.

The nonlimiting examples which are given below by way of illustration will enable better understanding of the invention.

EXAMPLES 1 to 82

Examples 1 to 82 relate to tests of the biocidal composition according to the invention in treatment by injection into the water.

A) Materials employed

1 Polyamines

Table I below gives the distribution of fatty chains in the commercial polyamines used. The first column of Table I gives the commercial name of the polyamine; for example, "tallow" denotes a polyamine whose fatty chain R₁ is derived from tallow, and "octyl" denotes a commercial polyamine derived from industrial octanoic acid.

                                      TABLE I                                      __________________________________________________________________________                AVERAGE COMPOSITION OF FATTY CHAINS                                            % by weight                                                         CHAINS     C8 C10 C12 C14 C16                                                                               C16.1*                                                                             C18 C18.1*                                    __________________________________________________________________________     Octyl or capryl                                                                           98 2                                                                Decyl         >90                                                              Dodecyl or lauryl                                                                            1-2 96-98                                                                              1-3                                                      Tetradecyl or myristyl                                                                           2-4 92-96                                                                              2-4                                                  Octadecyl or stearyl      7-10   90                                            Coconut    3-7                                                                               5-7 48-54                                                                              18-20                                                                              9-14                                                                              8-12                                                                               2-8 4-6                                       Tallow                4-5 30     20-21                                                                              45                                        Oleyl             0-1 0-4 5-12                                                                              6   10  70-72                                     __________________________________________________________________________      *C16.1 = hexadecenyl chain                                                     C18.1 = octadecenyl chain                                                

2 -Macroorganisms

Adult Dreissena (Dreissena polymorpha pallas) (18 to 23 mm in length) were collected in the Moselle. The molluscs are kept in the laboratory in dechlorinated and permanently aerated mains water suitable for drinking under the following conditions:

temperature: 18° C.±1° C.

pH: 7.6-8.2.

The Dreissena are fed daily with green algae of the genus Chlamydomonas, which have been frozen beforehand. The cubes of frozen algae are suspended above the experimentation vessels and distribute the algae gradually, as they melt.

B Methods

Mortality tests: The adult Dreissena (18-23 mm) are acclimatized to laboratory conditions for three days, during which they become attached to the support (a glass plate).

The experimental set-up consists of 12-liter vessels which are fed continuously (flow rate: 100 ml/min) with drinkable mains water which has been dechlorinated beforehand. The water in the vessels is permanently aerated and the medium is homogenized with a pump operating in closed circuit (flow rate: 6/min).

50 Dreissena make up the initial experimental sample for each support and each concentration tested. Each sample is subjected to daily injections of 90 minutes or 180 minutes so as to obtain concentrations of 2, 6 and 10 mg of composition per liter of water in the vessels, and this is repeated for each composition so as to determine the optimum efficacy.

The mortality is evaluated daily for one month; it is established when the Dreissena maintain their valves open and no longer respond to a tactile stimulus.

The control sample is subjected to the same experimental conditions but is maintained exclusively in dechlorinated drinkable mains water.

To determine the existence of a molluscicidal synergy for the mixture of two substances tested, the method used was that proposed by Ku F. C., Eismann P. C., Sylvestrowicz H. D., Mayer R. L. (1961), Appl. Microbiol. 9, 538-541, in order to determine the biostatic synergy. The formula used is as follows: ##EQU1## in which: CA is the minimum molluscicida concentration of substance A

QA is the quantity of substance A in the minimum molluscicidal concentration of the mixture A/B

CB is the minimum molluscicidal concentration of the substance B

QB is the quantity of substance B in the minimum molluscicidal concentration of the mixture A/B.

When X=1, there is additivity of the effects; when X>1, there is antagonism; and, when X<1, there is synergy.

The compositions were prepared in the form of microemulsions by mixing one or more polyamines with 2-amino-2-methyl-1-propanol and an ethoxylated amine, as emulsifying surfactants, and water. Genamin® O-200 is an oleylamine which carries 20 units of ethylene oxide.

Table 2 gives, by way of comparison, the optimum molluscicidal concentrations for various polyamines used by themselves.

                                      TABLE 2                                      __________________________________________________________________________                          EXAMPLES                                                                       1  2  3  4  5  6  7  8  9                                 PRODUCTS             COMPOSITION IN % BY WEIGHT                                __________________________________________________________________________     N-octylamine         10                                                        N-decylamine            10                                                     N-dodecylamine             10                                                  N-tetradecylamine             10                                               N-hexadecylamine                 10                                            N-oleylamine                        10                                         N-octadecylamine                       10                                      N-erucidylamine                           10                                   N-behenylamine                               10                                2-amino-2-methyl-1-propanol                                                                         2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                               GENAMIN ® O-200  2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                               WATER                85 85 85 85 85 85 85 85 85                                MOLLUSCICIDAL CONCENTRATION                                                                         10 8  8  10 11 9  11 13 14                                __________________________________________________________________________                          EXAMPLES                                                                       11 12 13 14 15 16 17 18 19                                PRODUCTS             COMPOSITION IN % BY WEIGHT                                __________________________________________________________________________     N-octyl-1,3-propylenediamine                                                                        10                                                        N-decyl-1,3-propylenediamine                                                                           10                                                     N-dodecyl-1,3-propylenediamine                                                                            10                                                  N-tetradecyl-1,3-propylenediamine                                                                            10                                               N-hexadecyl-1,3-propylenediamine 10                                            N-oleyl-1,3-propylenediamine        10                                         N-octadecyl-1,3-propylenediamine       10                                      N-coconut-1,3-propylenediamine            10                                   N-tallow-1,3-propylenediamine                10                                2-amino-2-methyl-1-propanol                                                                         2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                               GENAMIN ® O-200  2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                               WATER                85 85 85 85 85 85 85 85 85                                MOLLUSCICIDAL CONCENTRATION                                                                         8  6  6  8  10 8  9  6  8.5                               __________________________________________________________________________

It can be seen from Table 2 that the various amines and diamines, used on their own, have a molluscicidal action.

Table 3 gives the molluscicidal action of various mixtures of diamines.

                                      TABLE 3                                      __________________________________________________________________________                  EXAMPLES                                                                       20 21 22  23 24 25  26 27 28  29                                  PRODUCTS     COMPOSITION IN % BY WEIGHT                                        __________________________________________________________________________     N-dodecyl-1,3-propylene-                                                                    8  6  5   4  2  8   6  5  4   2                                   diamine                                                                        N-tetradecyl-1,3-                                                                           2  4  5   6  8  --  -- -- --  --                                  propylene-diamine                                                              N-oleyl-1,3-propylene-                                                                      -- -- --  -- -- 2   4  5  6   8                                   diamine                   --                                                   2-amino-2-methyl-1-                                                                         2.5                                                                               2.5                                                                               2.5 2.5                                                                               2.5                                                                               2.5 2.5                                                                               2.5                                                                               2.5 2.5                                 propanol                                                                       GENAMIN ® O-200                                                                         2.5                                                                               2.5                                                                               2.5 2.5                                                                               2.5                                                                               2.5 2.5                                                                               2.5                                                                               2.5 2.5                                 WATER        85 85 85  85 85 85  85 85 85  85                                  MOLLUSCICIDAL                                                                               6.5                                                                               7  7   7.5                                                                               7.5                                                                               6.1 6.0                                                                               6.1                                                                               6.4 7.1                                 CONCENTRATION                                                                  VALUE of X   1  1  1   1  1  0.96                                                                               0.90                                                                              0.89                                                                              0.91                                                                               0.96                                __________________________________________________________________________                  EXAMPLES                                                                       30 31 32  33 34 35  36 37 38  39                                  PRODUCTS     COMPOSITION IN % BY WEIGHT                                        __________________________________________________________________________     N-dodecyl-1,3-propylene-                                                                    -- -- --  -- -- --  -- -- --  --                                  diamine                                                                        N-tetradecyl-1,3-                                                                           8  6  5   4  2  --  -- -- --  --                                  propylene-diamine                                                              N-oleyl-1,3-propylene-                                                                      2  4  5   6  8  1   2  2  4   5                                   diamine                                                                        N-coconut-1,3-propylene-                                                                    -- -- --  -- -- 9   8  7  6   5                                   diamine                                                                        2-amino-2-methyl-1-                                                                         2.5                                                                               2.5                                                                               2.5 2.5                                                                               2.5                                                                               2.5 2.5                                                                               2.5                                                                               2.5 2.5                                 propanol                                                                       GENAMIN ® O-200                                                                         2.5                                                                               2.5                                                                               2.5 2.5                                                                               2.5                                                                               2.5 2.5                                                                               2.5                                                                               2.5 2.5                                 WATER        85 85 85  85 85 85  85 85 85  85                                  MOLLUSCICIDAL                                                                               7.6                                                                               7.1                                                                               7.1 7.4                                                                               7.7                                                                               5.9 6.0                                                                               5.9                                                                               5.6 5.7                                 CONCENTRATION                                                                  VALUE of X   0.95                                                                              0.88                                                                              0.89                                                                               0.92                                                                              0.96                                                                              0.97                                                                               0.96                                                                              0.94                                                                              0.88                                                                               0.88                                __________________________________________________________________________                  EXAMPLES                                                                       40 41 42 43 44 45 46 47 48 49 50                                  PRODUCTS     COMPOSITION IN % BY WEIGHT                                        __________________________________________________________________________     N-coconut-1,3-propylene-                                                                    4  3  2  9  8  7  6  5  4  3  2                                   diamine                                                                        N-oleyl-1,3-propylene-                                                                      6  7  8  -- -- -- -- -- -- -- --                                  diamine                                                                        N-tallow-1,3-propylene-                                                                     -- -- -- 1  2  3  4  5  6  7  8                                   diamine                                                                        2-amino-2-methyl-1-                                                                         2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                 propanol                                                                       GENAMIN ® O-200                                                                         2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                 WATER        85 85 85 85 85 85 85 85 85 85 85                                  MOLLUSCICIDAL                                                                               5.9                                                                               6.1                                                                               6.4                                                                               5.9                                                                               6.1                                                                               6.2                                                                               6.1                                                                               6.4                                                                               6.8                                                                               7.2                                                                               7.5                                 CONCENTRATION                                                                  VALUE of X   0.90                                                                              0.91                                                                              0.94                                                                              0.95                                                                              0.96                                                                              0.94                                                                              0.89                                                                              0.91                                                                              0.93                                                                              0.95                                                                              0.96                                __________________________________________________________________________

This table shows that the mixture of dodecylpropylenediamine and of tetradecylpropylenediamine has no synergetic effect on the molluscicidal action, but that, when the mixture contains an octadecenyl (C81.1) propylenediamine, there is synergy (X is less than 1).

Table 4 indicates the molluscicidal concentrations in the presence of triamines and tetramines on their own (Examples 52 to 55) or as a mixture with other polyamines (Examples 51 and 53 to 65).

                                      TABLE 4                                      __________________________________________________________________________                    EXAMPLES                                                                       51 52 53  54 55  56 57                                          PRODUCTS       COMPOSITION IN % BY WEIGHT                                      __________________________________________________________________________     N-coconut-1,3-propylene-        5  5                                           diamine                                                                        N-coconut-[NH(CH.sub.2).sub.3 ].sub.2 NH.sub.2                                                10                                                              N-oleyl-[NH(CH.sub.2).sub.3 ].sub.2 NH.sub.2                                                     10            5                                              N-tallow-[NH(CH.sub.2).sub.3 ].sub.2 NH.sub.2                                                       10                                                        N-coconut-[NH(CH.sub.2).sub.3 ].sub.3 NH.sub.2                                                          10                                                    N-oleyl-[NH(CH.sub.2).sub.3 ].sub.3 NH.sub.2                                                               10     5                                           2-amino-2-methyl-1-                                                                           2.5                                                                               2.5                                                                               2.5 2.5                                                                               2.5 2.5                                                                               2.5                                         propanol                                                                       GENAMIN ® O-200                                                                           2.5                                                                               2.5                                                                               2.5 2.5                                                                               2.5 2.5                                                                               2.5                                         WATER          85 85 85  85 85  85 85                                          MOLLUSCICIDAL  6.5                                                                               7  8   6  7   6.4                                                                               6.2                                         CONCENTRATION                                                                  VALUE of X     -- -- --  -- --  0.96                                                                              0.93                                        __________________________________________________________________________                    EXAMPLES                                                                       58 59 60 61 62 63 64 65                                         PRODUCTS       COMPOSITION IN % BY WEIGHT                                      __________________________________________________________________________     N-coconut-1,3-propylene-   8  2     3                                          diamine                                                                        N-oleyl-1,3-propylenediamine                                                                  5  5     4        8                                             N-coconut-[NH(CH.sub.2).sub.3 ].sub.2 NH.sub.2                                                5     5  6        2                                             N-coconut-[NH(CH.sub.2).sub.3 ].sub.3 NH.sub.2                                                   5                 7                                          N-oleyl-[NH(CH.sub.2).sub.3 ].sub.3 NH.sub.2                                                        5     2  8                                                2-amino-2-methyl-1-propanol                                                                   2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                        GENAMIN ® O-200                                                                           2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                        WATER          85 85 85 85 85 85 85 85                                         MOLLUSCICIDAL  6.3                                                                               6.1                                                                               6.4                                                                               6.1                                                                               5.9                                                                               6.8                                                                               6.4                                                                               6.9                                        CONCENTRATION                                                                  VALUE of X     0.93                                                                              0.94                                                                              0.92                                                                              0.91                                                                              0.94                                                                              0.93                                                                              0.93                                                                              0.97                                       __________________________________________________________________________

Table 4 shows that there is also synergy when the oleyl polyamine is a triamine or a tetramine.

The tests compiled in Table 5 were carried out in the presence of different solvents and different emulsifying surfactants.

                                      TABLE 5                                      __________________________________________________________________________                     EXAMPLES                                                                       66 67  68 69  70 71  72 73                                     PRODUCTS        COMPOSITION IN % BY WEIGHT                                     __________________________________________________________________________     N-coconut-1,3-propylene-                                                                       4  4   4  4   4  4   4  4                                      diamine                                                                        N-oleyl-1,3-propylene-                                                                         6  6   6  6   6  6   6  6                                      diamine                                                                        DIETHYLENE GLYCOL                                                                              10                                                             HEXYLENE GLYCOL    10            10  10                                        MONOPROPYLENE GLYCOL   10               10                                     2-amino-2-methyl-1-                                                                            2.5                                                                               2.5 2.5                                                                               2.5 2.5                                                                               2.5 2.5                                                                               2.5                                    propanol                                                                       GENAMIN ® S-200*                                                                           2.5                                                                               2.5 2.5                                                     GENAMIN ® O-250*      2.5    2.5                                           GENAMIN ® T-200*          2.5       2.5                                    GENAMIN ® T-250*                 2.5                                       WATER           75 75  75 85  85 75  75 75                                     MOLLUSCICIDAL   6  6   6  6.2 6.1                                                                               6.2 6.2                                                                               6.1                                    CONCENTRATION                                                                  VALUE of X      0.91                                                                              0.91                                                                               0.91                                                                              0.94                                                                               0.93                                                                              0.94                                                                               0.94                                                                              0.93                                   __________________________________________________________________________                     EXAMPLES                                                                       74 75 76 77 78 79 80 81 82                                     __________________________________________________________________________     PRODUCTS        COMPOSITION IN % BY WEIGHT                                     __________________________________________________________________________     N-coconut-1.3-propylene-                                                                       4  4  4  4  4  4  4  4  4                                      diamine                                                                        N-oleyl-1,3-propylene-                                                                         6  6  6  6  6  6  4  6  6                                      diamine                                 50                                     DIETHYLENE GLYCOL        50 50 50 50 50                                        HEXYLENE GLYCOL                   2  2.5                                       MONOPROPYLENE GLYCOL           2  0.5                                                                               0.5                                       2-amino-2-methyl-1-                                                                            2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               2.5                                                                               0.5      2.5                                    propanol                                                                       2-diethylamino-1-ethanol                                                                          2.5      2.5                                                GENAMIN ® S-200*                                                                           2.5      2.5            2.5                                    GENAMIN ® O-250*  2.5            2.5                                       GENAMIN ® T-200*           2.5                                                                               2.5                                          GENAMIN ® T-250*                                                                           85 85 85 35 35 35 35 35 35                                     WATER                                                                          MOLLUSCICIDAL   6.2                                                                               6  6.1                                                                               6.2                                                                               6  6.2                                                                               6.2                                                                               6.1                                                                               6.2                                    CONCENTRATION                                                                  VALUE of X      0.94                                                                              0.91                                                                              0.93                                                                              0.94                                                                              0.91                                                                              0.94                                                                              0.94                                                                              0.93                                                                              0.94                                   __________________________________________________________________________      *Genamin S200: soya amine containing 20 units of ethylene oxide                Genamin O250: olein amine containing 25 units of ethylene oxide                Genamin T200: tallow amine containing 20 units of ethylene oxide               Genamin T250: tallow amine containing 25 units of ethylene oxide         

Table 5 shows that the different solvents and the different emulsifying surfactants have virtually no effect on the molluscicidal action of the polyamines.

EXAMPLES 83 to 138

Examples 83 to 138 relate to tests of a bioactive paint for treatment by application to the surfaces in contact with the water.

A) Method

A series of bioactive paints was made which contained compositions based on long-chain amines, which were introduced into a coating composition corresponding to the following formulation, expressed by dry weight:

    ______________________________________                                         Vinyl resin     27 parts by weight                                             Shellac         33 parts by weight                                             Tricresyl phosphate                                                                            10 parts by weight                                             Red iron oxide   5 parts by weight                                             Bioactive filler*                                                                              25 parts by weight                                             ______________________________________                                          *Bioactive filler = 50% by weight of amines + 50% by weight of Sylobloc 4      ® (micronized silica)                                                

The bioactive filler is a powder obtained by mixing the amine, in the liquid state, with Sylobloc 45® in a high-shear turbine.

The composition of the bioactive filler is represented by compositions 83 to 138. The bioactive coating was obtained by incorporating the bioactive filler into the formulation above. The components of the formulation were dispersed beforehand, using a high-shear turbine, with a mixture of 30% by weight of solvent comprising xylene/Solvesso 100 (72/28 by weight), at a speed of 20,000 revolutions per minute so as to obtain a fine and homogeneous dispersion, before introduction of the bioactive filler.

150×®×1.5 mm steel plates were sanded on both sides and then coated with each bioactive formulation in two layers representing, after drying, a total layer of 80 microns in thickness; the control plates were treated in the same way, although the formulation contained only "Sylobloc 45 " silica as filler, with no bioactive amine.

Two series of plates were then immersed in the sea in the sub-tropical zone, suspended by nylon threads at a depth of 1 metre in one case and 10 metres in the other case, in order to determine the anti-fouling properties. The immersion tests were carried out for an initial period of 1 month in January: the plates were then withdrawn and compared with the control plates; after weighing, the deposits attached to the plates were removed for identification and counting of the species deposited per m². A new series of coated plates was immersed under the same conditions for a period of three months with three repeats in February, May, August and October, and then examined again by comparison with the control plates.

Table 6 indicates the most important of the various species which became attached principally to the series of plates immersed as controls.

                                      TABLE 6                                      __________________________________________________________________________     SPECIES                                                                                     (POLYCHAETES)                                                                            (CIRRIPEDES)                                            ALGAE  BRYOZOA                                                                              SERPULAE  CRUSTACEANS                                                                             ASCIDIANS                                                                             AMPHIPODS                                                                             HYDROZOA                         __________________________________________________________________________     Rhizoclonium                                                                          Bugula                                                                               Hydroides Balanus  Cyona  Ericthnius                                                                            Tubularia                        riparium                                                                              neritina                                                                             norvegica amphitrite                                                                              intestinalis                                                                          pugnax mesembry-                        and                    variegatus             anthenum                         Enteromorpha           trigonus                                                prolifera                                                                      __________________________________________________________________________

B Results

The inhibitory activity of the various compositions with regard to marine fouling was evaluated as a function of the weight and number of the various species deposited on the experimental plates immersed close to the surface and at a depth, at the end of the various periods of immersion. Table 7 shows the efficacy, expressed in %, for each composition of bioactive filler introduced into the coating formula. The efficacy is calculated as follows: the weight of microorganisms on each treated plate and on the control plate is measured, and the weight difference is calculated. The efficacy is expressed in per cent. The value given is the arithmetic mean of the values obtained.

It is evident that the mixtures of polyamines derived from coconut with polyamines derived from tallow or oleyl polyamines are more effective as marine anti-fouling agents than the pure amines taken individually, as shown by the results given in Table 7.

                                      TABLE 7                                      __________________________________________________________________________                  EXAMPLES                                                                       83                                                                               84                                                                               85  86                                                                               87  88                                                                               89  90                                                                               91  92                                      PRODUCTS     COMPOSITION IN % BY WEIGHT                                        __________________________________________________________________________     N-octylamine 50                                                                N-decylamine   50                                                              N-tetradecylamine                                                                               50                                                            N-hexadecylamine     50                                                        N-oleylamine           50                                                      N-octadecylamine           50                                                  N-octyl-1,3-propylene-       50                                                diamine                                                                        N-decyl-1,3-propylene-           50                                            diamine                                                                        N-dodecyl-1,3-propylene-           50                                          diamine                                                                        N-tetradecyl-1,3-                      50                                      propylenediamine                                                               Sylobloc 45  50                                                                               50                                                                               50  50                                                                               50  50                                                                               50  50                                                                               50  50                                      EFFICACY in %                                                                                5                                                                               10                                                                               30  20                                                                               17  15                                                                                5  12                                                                               30  25                                      __________________________________________________________________________              EXAMPLES                                                                       93 94                                                                               95  96                                                                               97  98                                                                               99  100                                                                               101  102                                      PRODUCTS COMPOSITION IN % BY WEIGHT                                            __________________________________________________________________________     N-hexadecyl-1,3-                                                                        50                                                                    propylenediamine                                                               N-oleyl-1,3-                                                                               50      50                                                         propylenediamine                                                               N-octadecyl-1,3-                                                                             50                                                               propylenediamine                                                               N-coconut-1,3-    50                                                           propylenediamine                                                               N-tallow-1,3-           50                                                     propylenediamine                                                               N-dodecyl-1,3-            40  30 25   20                                       propylenediamine                                                               N-tetradecyl-1,3-         10  20 25   30                                       propylenediamine                                                               Sylobloc 45                                                                             50 50                                                                               50  50                                                                               50  50                                                                               50  50 50   50                                       EFFICACY in %                                                                           15 20                                                                               10  25                                                                               20  15                                                                               20  20 25   20                                       __________________________________________________________________________              EXAMPLES                                                                       103 104                                                                               105 106                                                                               107 108                                                                               109 110                                                                               111                                       PRODUCTS COMPOSITION IN % BY WEIGHT                                            __________________________________________________________________________     N-dodeceyl-1,3-                                                                         10  40 30  25 20                                                      propylenediamine                                                               N-tetradecyl-1,3-                                                                       40                40 30  25 20                                        propylenediamine                                                               N-oleyl-1,3- 10 20  25 30  10 20  25 30                                        propylenediamine                                                               Sylobloc 45                                                                             50  50 50  50 50  50 50  50 50                                        EFFICACY in %                                                                           25  50 55  50 40  40 45  45 40                                        __________________________________________________________________________              EXAMPLES                                                                       112 113                                                                               114 115                                                                               116 117                                                                               118 119                                                                               120                                       PRODUCTS COMPOSITION IN % BY WEIGHT                                            __________________________________________________________________________     N-coconut-1,3-                                                                          45  40 30  25 20   5 45  40 35                                        propylenediamine                                                               N-oleyl-1,3-                   5  10 15                                        propylenediamine                                                               N-tallow-1,3-                                                                            5  10 20  25 30  45                                                  propylenediamine                                                               Sylobloc 45                                                                             50  50 50  50 50  50 50  50 50                                        EFFICACY in %                                                                           50  45 55  50 40  37 45  30 55                                        __________________________________________________________________________                   EXAMPLES                                                                       121                                                                               122                                                                               123                                                                               124                                                                               125                                                                               126                                                                               127                                                                               128                                                                               129                                      PRODUCTS      COMPOSITION IN % BY WEIGHT                                       __________________________________________________________________________     N-coconut-1,3-                                                                               30 25 20 15 10                                                   propylenediamine                                                               N-oleyl-1,3-  20 15 30 35 40                                                   propylenediamine                                                               N-dodecyl-[NH(CH.sub.2).sub.3 ].sub.2--NH.sub.2                                                             50                                                N-coconut-[NH(CH.sub.2).sub.3 ].sub.2--NH.sub.2                                                                50                                             N-oleyl-[NH(CH.sub.2).sub.3 ].sub.2--NH.sub.2                                                                     50                                          N-tallow-[NH(CH.sub.2).sub.3 ].sub.2--NH.sub.2                                                                       50                                       Sylobloc 45   50 50 50 50 50 50 50 50 50                                       EFFICACY in % 55 65 45 40 40 40 30 30 25                                       __________________________________________________________________________                   EXAMPLES                                                                       130                                                                               131                                                                               132                                                                               133                                                                               134                                                                               135                                                                               136                                                                               137                                                                               138                                      PRODUCTS      COMPOSITION IN % BY WEIGHT                                       __________________________________________________________________________     N-coconut-1,3-         25 25                                                   propylenediamine                                                               N-oleyl-1,3-                 25 25    20                                       propylenediamine                                                               N-coconut-[NH(CH.sub.2).sub.3 ].sub.2--NH.sub.2                                                             25    25 30                                       N-oleyl-[NH(CH.sub.2).sub.3 ].sub.2--NH.sub.2                                                         25                                                      N-coconut-[NH(CH.sub.2).sub.3 ].sub.3--NH.sub.2                                              50                25                                             N-oleyl-[NH(CH.sub.2).sub.3 ].sub.3--NH.sub.2                                                   50       25       25                                          N-tallow-[NH(CH.sub.2).sub.3 ].sub.3--NH.sub.2                                               50                                                               Sylobloc 45   50 50 50 50 50 50 50 50 50                                       EFFICACY in % 35 30 35 50 45 45 40 40 50                                       __________________________________________________________________________

After a period of one month, the mean percentage mortality remains very low in the control group, indicating that the mortality recorded in the groups exposed to the treatment according to the invention does indeed result from the molluscicidal action tested. 

I claim:
 1. A biocidal or biostatic composition containing an active agent comprising a mixture of amines containing at least one polyamine of the formula (I)

    R.sub.1 -NH[(CH.sub.2).sub.3 -NH].sub.n -(CH.sub.2).sub.3 NH.sub.2(I)

in which n is an integer from 0 to 3 and R₁ is a dodecyl radical or at least one polyamine of formula (I) wherein R₁ is an tetradecyl radical, or a mixture thereof, at least one polyamine of formula (I) wherein R₁ is an octadecenyl radical and at least one monoamine of the formula (II):

    R.sub.2 NH.sub.2                                           (II)

wherein R₂ is an octadecenyl radical.
 2. The composition according to claim 1 wherein said polyamines are derived from at least one of tallow, or vegetable or animal oil containing olein with at least one of said polyamines being derived from coconut.
 3. The composition according to claim 1 wherein said active agent contains not more than 15% by weight of said at least one amine of formula (II).
 4. The composition according to claim 1 wherein said composition is an aqueous emulsion.
 5. The composition according to claim 4 further comprising an emulsifier comprising at least one polyoxyethylenated tertiary amine of formula (III): ##STR2## in which formula R₃ is a C₈ -C₂₂ alkyl or alkenyl radical and x and y are integers such that (x+y) is from 5 to
 50. 6. The composition according to claim 5 wherein the emulsifier is present in an amount of from 5 to 45% by weight relative to said active agent.
 7. The composition according to claim 4 wherein the aqueous phase of said emulsion contains at least one organic solvent selected from the group consisting of at least one organic solvent selected from the group consisting of diethylene glycol, hexylene glycol, monopropylene glycol and an amino alcohol of formula IV:

    HO-A-NR.sub.4 R.sub.5                                      (IV)

in which A is a C₂ -C₄ linear or branched alkenyl radical and R₄ and R₅, which are identical or different, are H or a C₁ -C₃ alkyl radical. 